Azodyes containing a bridge member based on diamino-substituted triazines

ABSTRACT

Dye mixtures which comprise at least one anionic acid dye of the formula   &lt;IMAGE&gt; (1)  together with at least one anionic acid dye of the formula   &lt;IMAGE&gt; (2)  in which the substituents are as defined in claim 1, and the novel dyes of the formulae (1) and (2) are direct dyes for cellulosic fibre materials in particular. They have a high heat stability and are particularly suitable for one-bath, one-stage dyeing of polyester/cotton blend fabrics with a disperse dye for the polyester fibres under the dyeing conditions for polyester fibres.

The present invention relates to novel mixtures of azo dyes, novel azo dyes, processes for their preparation and their use for dyeing and printing fibre materials, in particular textile fibre materials.

The object on which the present invention was based was to discover dye mixtures and dyes which are suitable for dyeing fibre materials containing nitrogen and fibre materials containing hydroxyl groups, in particular cellulosic fibre materials, have good fastness properties and have a high heat stability.

It has now been found that the following azo dye mixtures and azo dyes meet these requirements.

The present invention relates to dye mixtures which comprise at least one anionic acid dye of the formula ##STR3## together with at least one anionic acid dye of the formula ##STR4## in which R₁, R₂, R₃, R₄, R₅ and R₆ independently of one another are hydrogen or C₁ -C₄ alkyl, B₁ and B₂ independently of one another are an aliphatic or aromatic bridge member, A₁, A₂, A₃, A₄, A₅ and A₆ independently of one another are the radical of a monoazo- or disazo dye or the radical of a metal complex azo dye,

n is the number 0 or 1 and

Y₁ and Y₂ independently of one another are a radical of the formula ##STR5## in which R₇, R₈ and R₈ ' independently of one another are hydrogen or substituted or unsubstituted C1-C₈ alkyl and

E₁ is substituted or unsubstituted C₂ -C₈ alkylene which is uninterrupted or interrupted by one or more groups -O-, or substituted or unsubstituted C₅ -C₇ cycloalkylene, C₅ -C₇ -cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ -cycloalkylene.

C₁ -C₄ Alkyl R₁, R₂, R₃, R₄, R₅ and R₆ is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, in particular methyl or ethyl, preferably methyl.

Preferably, R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen, methyl or ethyl, in particular hydrogen.

C₁ -C₈ Alkyl R₇, R₈ and R₈ ' is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, or straight-chain or branched pentyl, hexyl, heptyl or octyl. C₁ -C₈ Alkyl radicals R₇, R₈ and R₈ ' can be further substituted, for example by hydroxyl, C₁ -C₄ alkoxy, halogen, amino or sulfato, in particular by hydroxyl, C₁ -C₄ alkoxy or amino.

Preferably, R₇, R₈ and R₈ ' are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl, C₁ -C₄ alkoxy or amino.

The C₂ -C₈ alkylene radical E₁ can be interrupted by one or more groups -O-, in particular by one to three, and preferably by one or two groups -O-. The radicals which are not interrupted by a group -O- are preferred. Possible substituents for the C₂ -C₈ alkylene radical E₁ are, for example, hydroxyl, C₁ -C₄ alkoxy, halogen, amino or sulfato, in particular hydroxyl or C₁ -C₄ alkoxy. Examples of such C₂ -C₈ alkylene radicals are 1,2-ethylene, 1,2-propylene, 1,3-propylene and 1,3-propylene which is substituted by hydroxyl in the 2-position.

The C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylen-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene radical E₁ can be substituted in the alkylene radical, for example by hydroxyl or C₁ -C₄ alkoxy and in the cycloalkyl ring, for example by C₁ -C₄ alkyl, in particular by methyl. Alkyl is to be understood here as meaning, in particular, cyclohexyl. C₅ -C₇ Cycloalkylene-C₁ -C.sub. alkylene and C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene are, in particular, cyclohexylene-methylene and methylene-cyclohexylene, which can be substituted by C₁ -C₄ alkyl in the cyclohexyl ring.

The radical E₁ is preferably C₂ -C₈ alkylene, which is as defined and preferred above.

The radicals Y₁ and Y₂ preferably have identical meanings.

Aliphatic or aromatic bridge members for B₁ and B₂ are, for example, the following: ##STR6## in which

R₉, R₁₀ and R₁₁ independently of one another are hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy,

R₁₂ and R₁₂ ' independently of one another are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen, sulfo or carboxyl and

E₂ and E₃ independently of one another are C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene which are unsubstituted or substituted by C₁ -C₄ alkyl in the cycloalkyl ring,

R₉, R₁₀ and R₁₁ are preferably hydrogen, methyl or ethyl, in particular hydrogen.

R₁₂ and R₁₂ ' are preferably hydrogen or sulfo. In the bridge member of the formula (5h), R₁₂ and R₁₂ ' are preferably sulfo.

The C₂ -C₈ alkylene radicals E₂ and E₃ can be interrupted by one or more groups -O-, in particular by one to three, and preferably by one or two groups -O-. The radicals which are not interrupted by a group -O- are preferred. Possible substituents for the C₂ -C₈ alkylene radicals E₂ and E₃ are, for example, hydroxyl, C₁ -C₄ alkoxy, halogen, amino or sulfato, in particular hydroxyl or C₁ -C₄ alkoxy. Examples of such C₂ -C₈ alkylene radicals are 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,3-propylene which is substituted by hydroxyl in the 2-position and the radical of the formula --(CH₂)₃ --O--(CH₂)₄ --O--(CH₂)₃ --.

The C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene radicals E₂ and E₃ can be substituted in the alkylene radical, for example by hydroxyl or C₁ -C₄ alkoxy, and in the cycloalkyl ring, for example by C₁ -C₄ alkyl, in particular by methyl. Cycloalkyl here is understood as meaning, in particular, cyclohexyl. C₅ -C₇ Cycloalkylene-C₁ -C₈ alkylene and C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene are, in particular, cyclohexylene-methylene and methylene-cyclohexylene, which can be substituted by C₁ -C₄ alkyl in the cyclohexyl ring.

The radicals E₂ and E₃ are preferably C₂ -C₈ alkylene, which is as defined and preferred above.

Particularly preferred bridge members B₁ and B₂ are those of the formulae (5a), (5b), (5c) and (5h), in particular those of the formulae (5a), (5b) and (5c).

Radicals A₁, A₂, A₃, A₄, A₅ and A₆ of a monoazo or dis azo dye or of a metal complex azo dye preferably contain diazo components and coupling components of the benzene or naphthalene series. Metal complex azo dyes are, in particular, copper complex azo dyes.

Substituents of the radicals A₁, A₂, A₃, A₄, A₅ and A₆ are the customary substituents for azo dyes. Examples are the following: sulfo; carboxyl; hydroxyl; carbamoyl; cyano; amino; halogen, for example fluorine or, in particular, chlorine; ureido which is unsubstituted or mono- or disubstituted by C₁ -C₄ alkyl in the terminal amino group; C₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted or substituted by hydroxyl;

C₂ -C₆ alkanoylamino which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy in the alkyl part; and phenylamino or benzoylamino which are unsubstituted or substituted by C₁ -C₄ alkyl, C₂ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, carboxyl, halogen, cyano or ureido in the phenyl ring.

The radicals A₁, A₂, A₃, A₄, A₅ and A₆ are preferably those of the formula ##STR7## in which R₁₃, R₁₄, R₁₅ and R₁₆ independently of one another are hydrogen, sulfo, carboxyl, carbamoyl, halogen, cyano or ureido, C₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted or substituted by hydroxyl, or C₂ -C₄ alkanoylamino which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy in the alkyl part; ##STR8## in which R₁₇, R₁₈ and R₁₉ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR9## in which R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR10## in which R₂₅ and R₂₆ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR11## in which R₂₇ is hydrogen, C₂ -C₆ alkanoyl which is unsubstituted or substituted by hydroxyl or

C₁ -C₄ alkoxy, or phenyl or benzoyl which are unsubstituted or substituted by C₁ -C₄ alkyl,

C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, carboxyl, halogen, cyano or ureido in the phenyl ring, and

R₂₈ and R₂₉ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR12## in which R₃₀ and R₃₁ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR13## in which R₃₂ and R₃₃ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR14## in which R₃₄, R₃₅, R₃₆ and R₃₇ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; or ##STR15## in which R₃₈, R₃₉, R₄₀, R₄₁, R₄₂ and R₄₃ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆.

Preferred radicals of the formula (7) are those in which R₁₃, R₁₄, R₁₅ and R₁₆ independently of one another are hydrogen, sulfo, carboxyl, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

Preferred radicals of the formula (8) are those in which R₁₇, R₁₈ and R₁₉ are hydrogen, preferably at least one of these substituents being sulfo.

Preferred radicals of the formula (9) are those in which

R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ are hydrogen or sulfo, preferably at least one of these substituents being sulfo.

Preferred radicals of the formula (10) are those in which

R₂₅ and R₂₆ are hydrogen, sulfo or C₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted or substituted by hydroxyl.

Preferred radicals of the formula (11) are those in which

R₂₇ is benzoyl which is unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, carboxyl, halogen, cyano or ureido in the phenyl ring and R₂₉ and R₂₉ are hydrogen or sulfo.

Preferred radicals of the formula (12) are those in which

R₃₀ and R₃₀ are hydrogen or sulfo.

Preferred radicals of the formula (13) are those in which

R₃₂ and R₃₃ are hydrogen, sulfo, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

Preferred radicals of the formula (14) are those in which

R₃₄, R₃₅, R₃₆ and R₃₇ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₂ -C₄ alkanoylamino.

Preferred radicals of the formula (15) are those in which

R₃₈, R₃₉, R₄₀, R₄₁, R₄₂ and R₄₃ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₂ -C₄ alkanoylamino. Preferably, one of the radicals R₄₀ and R₄₁ here is sulfo.

Particularly preferred radicals A_(l), A₂, A₃, A₄, A₅ and A₆ are those of the formulae (6), (7), (8), (9), (10), (11), (12) and (14), preferably radicals of the formulae (6), (7), (9), (11), (12), and (14), in particular the radical of the formula (6) or (7),

The radicals A₃ and A₅ and the radicals A₄ and A₆ in the dyes of the formula (2) in each case preferably have identical meanings.

The radicals A₁ and A₂ in the dyes of the formula (1) preferably have identical meanings.

A₁, A₂, A₃, A₄, A₅ and A₆ particularly preferably have identical meanings.

n is preferably the number 0.

Preferred dye mixtures are those in which

R₇, R₈ and R₈ ' independently of one another are hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene which are unsubstituted or substituted by C₁ -C₄ alkyl in the cycloalkyl ring.

n here is preferably the number 0 and the radicals R₁, R₂, R₃, R₄, R₅ and R₆, B₁ and B₂, and A₁, A₂, A₃, A₄, A₅ and A₆ are as defined and preferred above.

Particularly preferred dye mixtures are those in which

R₇, R₈ and R₈ ' are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and

E₁ is C₂ -C₈ alkylene, which can be interrupted by one or two groups -O- and is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

n here is preferably the number 0 and the radicals R₁, R₂, R₃, R₄, R₅ and R₆, B₁ and B₂, and A₁, A₂, A₃, A₄, A₅ and A₆ are as defined and preferred above.

An interesting group of dye mixtures is formed by those which comprise an anionic acid dye of the formula ##STR16## together with an anionic acid dye of the formula ##STR17## in which X₁ is a radical of the formula ##STR18## in which R₇ and R₈ are hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and

E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ -cycloalkylene,

C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene which are unsubstituted or substituted by C₁ -C₄ alkyl in the cycloalkyl ring, and A₁, A₂, R₁ and R₂ are as defined and preferred above.

The radicals with identical designations in the dyes of the formulae (1a) and (2a) also have identical meanings here.

R₇ and R_(s) are preferably hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

E₁ is preferably C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

R₁ and R₂ are preferably hydrogen.

A₁ and A₂ are preferably radicals of the formulae (6) to (15), in particular those of the formulae (6), (7), (8), (9), (10), (11), (12) and (14), preferably those of the formula (6), (7), (9), (11), (12) and (14). A₁ and A₂ are particularly preferably radicals of the formula (6) or (7).

A₁ and A₂ preferably have identical meanings.

Preferred dye mixtures of the dyes of the formulae (1a) and (2a) are those in which R₇ and R₈ are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy,

E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and A₁ and A₂ in particular have identical meanings.

Particularly preferred dye mixtures of the dyes of the formulae (1a) and (2a) are those in which

R₇ and R₈ are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy,

E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy, R₁ and R₂ are hydrogen and

A₁ and A₂ are radicals of the formulae (6) to (15), in particular those of the formulae (6), (7), (8), (9), (10), (11), (12) and (14), preferably those of the formulae (6), (7), (9), (11), (12) and (14).

A₁ and A₂ here are particularly preferably radicals of the formula (6) or (7). A₁ and A₂ preferably have identical meanings.

Radicals X₁ of the formula (4a) are of particular interest.

The present invention furthermore relates to the novel anionic acid dyes of the formula (1) in which

R₁, R₂, B₁, A₁, A₂, Y₁, Y₂ and n are as defined and preferred above.

Preferred dyes of the formula (1) are those in which

R₁ and R₂ are hydrogen or C₁ -C₄ alkyl, in particular hydrogen,

B₁ is a bridge member of the formulae (5a) to (5h),

A₁ and A₂ are radicals of the formulae (6) to (15), in particular those of the formulae (6), (7), (8), (9), (10), (11), (12) and (14), preferably those of the formulae (6), (7), (9), (11), (12) and (14),

R₇, R₈ and R₈ ' are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and

E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

Radicals A₁ and A₂ of the formula (6) or (7) are of particular interest here. A₁ and A₂ preferably have identical meanings. n is, in particular, the number 0.

Particularly preferred dyes of the formula (1) in which

n is the number 0,

are those in which

R₁ and R₂ are hydrogen,

A₁ and A₂ are radicals of the formulae (7), (8), (9), (10), (11), (12) and (14), preferably those of the formulae (7), (9), (11), (12) and (14), and in particular those of the formula (7),

R₇, R₈ and R₈ ' are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and

E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy, and in which

the radicals A₁ and A₂ have identical meanings.

Especially preferred dyes of the formula (1) in which

n is the number 0,

are those in which

A₁ and A₂ are radicals of the formula (7), in particular radicals of the formula ##STR19## R₁, R₂ and Y₁ here are as defined and preferred above. R₁ and R₂ here are preferably hydrogen. Y₁ here is preferably a radical of the formula (3a) in which

R₇, R₈ and R₈ ', in particular, are hydrogen, and

E₁, in particular, is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

E₁ here is preferably C₂ -C₈ alkylene, in particular propylene.

Especially preferred dyes of the formula (1) in which

n is the number 1

are those in which

A₁ and A₂ are radicals of the formula (6), in particular radicals of the formula ##STR20## R₁, R₂, B₁, Y₁ and Y₂ here are as defined and preferred above. R₁ and R₂ here are preferably hydrogen. Y₁ and Y₂ here are preferably radicals of the formula (3e) in which R₈ and R₈ ', in particular, are hydrogen and

E₁, in particular, is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy.

E₁ here is preferably C₂ -C₈ alkylene, in particular ethylene.

B₁ here is preferably a radical of the formula (5d) in which R₉, R₁₀ and R₁₂ in particular are hydrogen.

The amino groups of the radical of the formula (5d) are preferably in the para-position relative to one another.

Another group of interesting dyes of the formula (1) is formed by the dyes of the formula (1a ) in which

R₁, R₂, X₁, A₁ and A₂ are as defined and preferred under formula (1a).

The present invention furthermore relates to novel anionic acid dyes of the formula (2) in which

R₃, R₄, R₅, R₆, B₂, A₃, A₄, A₅ and A₆ are as defined and preferred above.

Preferred dyes of the formula (2) are those in which

R₃, R₄, R₅ and R₆ are hydrogen or C₁ -C₄ alkyl, in particular hydrogen,

B₂ is a bridge member of the formulae (5a) to (5h), in particular a bridge member of the formulae (5a) to (5c), and

A₃, A₄, A₅ and A₆ are radicals of the formulae (6) to (15), in particular those of the formulae (6), (7), (8), (9), (10), (11), (12) and (14), preferably those of the formulae (6), (7), (9), (11), (12) and (14).

Radicals A₃, A₄, A₅ and A₆ of the formula (6) or (7) are of particular interest here.

Preferably, A₃ and A₅, and A₄ and A₆ in each case have identical meanings. Dyes which are of particular importance are those of the formula (2) in which A₃, A₄, A₅ and A₆ have identical meanings.

Particularly preferred dyes of the formula (2) are those in which

R₃, R₄, R₅ and R₆ are hydrogen,

B₂ is a bridge member of the formulae (5a) to (5c) and

A₃, A₄, A₅ and A₆ are radicals of the formulae (6), (7), (8), (9), (10), (11), (12), and (14), in particular those of the formulae (6), (7), (9), (11), (12) and (14), preferably those of the formula (6) or (7), and in which

A₃ and A₅, and A₄ and A₆ preferably in each case have identical meanings,

and in particular in which

A₃, A₄, A₅ and A₆ have identical meanings.

Another group of interesting dyes of the formula (2) is formed by the dyes of the formula (2a) in which

R₁, R₂, A₁, A₂ and X₁ are as defined and preferred under formula (2a).

The present invention furthermore relates to processes for the preparation of the dyes of the formulae (1) and (2).

The process for the preparation of anionic acid dyes of the formula (1) in which

n is the number 0

comprises reacting a compound of the formula ##STR21## with a compound of the formula

    A.sub.1 -NHR.sub.1                                         (19a),

a compound of the formula

    A.sub.2 -NHR.sub.2                                         (19b)

and a compound of the formula

    Y.sub.1 -H                                                 (20a)

in which

A₁, A₂, R₁, R₂ and Y₁ are each as defined under formula (1) and Z is halogen, preferably chlorine.

Preferably, the trihalogenotriazine compound of the formula (18) is first reacted with approximately stoichiometric amounts of an aminoazo compound of the formula (19a) at a temperature of -5° to 20° C., preferably 0° to 5° C., the pH being kept neutral to acid, preferably at 2 to 7, in particular 2 to 4, by addition of suitable bases, for example alkali metal bases, such as lithium hydroxide or carbonate, sodium hydroxide or carbonate or potassium hydroxide or carbonate. Approximately stoichiometric amounts of an aminoazo compound of the formula (19b) are advantageously added to the resulting reaction mixture and this is reacted with the triazine derivative at slightly elevated temperature, preferably at 30° to 60° C., and at a neutral to slightly acid pH, which is preferably 6 to 7. If the compounds of the formulae (19a) and (19b) are identical aminoazo compounds, about 2 equivalents of this aminoazo dye are reacted with one equivalent of triazine compound, the temperature preferably first being kept at -5° to 20° C. and then being increased to about 30° to 60° C.

Another possibility comprises reacting the triazine compound of the formula (18) with a mixture comprising both a compound of the formula (19a) and a compound of the formula (19b) which differs from this, a mixture which comprises an asymmetric compound of the formula ##STR22## and two symmetric compounds of the formulae ##STR23## being obtained.

The triazinyl dyes obtainable according to the processes described above still contain a halogen atom Z, which can be converted into a group Y₁ by reaction with a compound of the formula (20a) at elevated temperature, preferably 70° to 100° C., and at a neutral to slightly alkaline pH, which is, for example, 7 to 9, depending on the compound of the formula (20a) employed.

The compounds of the formula (1) defined above in which

n is the number 1

are prepared, for example, by

a) reacting, independently of one another, a compound of the formula ##STR24## with a compound of the formula

    A.sub.1 -NHR.sub.1                                         ( 19a)

to give the compound of the formula ##STR25## and reacting a further compound of the formula (18) with a compound of the formula

    A.sub.2 -NHR.sub.2                                         ( 19b)

to give the compound of the formula ##STR26## b) reacting a compound of the formula

    H-B.sub.1 -H                                               (22a)

in succession, in any sequence, with the compounds of the formula (21a) and (21b) obtainable according to a) and

c) reacting the compound obtainable according to b) of the formula ##STR27## with at least one of the compounds of the formulae

    Y.sub.1 -H (20a) and Y.sub.2 -H                            (20b)

in which

A₁, A₂, R₁, R₂, Y₁, Y₂ and B₁ are each as defined under formula (1) and

Z is halogen, preferably chlorine.

The reaction of the compound of the formula (18) with the compound of the formula (19a) and (19b) according to step a) is advantageously carried out here as described above.

The reaction of the compound of the formula (22a) with the compounds of the formula (21a) and (21b) obtained according to a) is preferably carded out at a slightly elevated temperature, advantageously, for example, at 30° to 50° C., and at a neutral to slightly acid pH, which is, for example, 6 to 7, approximately stoichiometric amounts of the compounds (21a), (21b) and (22a) being employed. If the compounds of the formula (19a) and (19b) are identical aminoazo compounds, 2 molar equivalents of the compound of the formula (21a) are advantageously first prepared and these are reacted with about 1 molar equivalent of a compound of the formula (22a). The compounds of the formula (23) obtainable according to b) still contain 2 halogen atoms Z, which can advantageously be converted into a group Y₁ or Y₂ as described above.

The process for the preparation of anionic acid dyes of the formula (2) comprises

a) reacting a compound of the formula ##STR28## with a compound of the formula

    A.sub.3 -NHR.sub.3                                         ( 19c)

and a compound of the formula

    A.sub.4 -NHR.sub.4                                         ( 19d)

to give the compound of the formula ##STR29## b) reacting a compound of the formula ##STR30## with a compound of the formula

    A.sub.5 -NHR.sub.5                                         ( 19e)

and a compound of the formula

    A.sub.6 -NHR.sub.6                                         ( 19f)

to give the compound of the formula ##STR31## and c) reacting a compound of the formula

    H-B.sub.2 -H                                               (22b)

with the compounds of the formula (24a) and (24b) obtainable according to a) and b), in which

A₃, A₄, A₅, A₆, R₃, R₄, R₅, R₆ and B₂ are each as defined under formula (2) and Z is halogen, preferably chlorine.

The reaction of the compound of the formula (18) with the compound of the formula (19c) and (19d) according to step a) and the reaction of the compound of the formula (18) with the compound of the formula (19e) and (19f) according to step b) is advantageously carried out here as described above.

The reaction of the compounds of the formulae (24a) and (24b) with the compound of the formula (22b) according to c) is preferably carded out at an elevated temperature, advantageously, for example, at 50° to 100° C., and at a neutral to slightly alkaline pH, which is, for example, 7 to 11, approximately stoichiometric amounts of the compounds (24a), (24b) and (22b) advantageously being employed. If the compounds of the formula (24a) and (24b) are identical aminoazo compounds, 2 molar equivalents of the compound of the formula (24a) are advantageously first prepared and these are reacted with about 1 molar equivalent of the compound of the formula (22b).

The present invention furthermore relates to a process for the preparation of dye mixtures which comprise an anionic acid dye of the formula (1a) together with an anionic acid dye of the formula (2a). This process comprises reacting a compound of the formula ##STR32## with a compound of the formula

    H-X.sub.1 -H                                               (17)

the compounds of the formulae (16) and (17) being in a molar ratio which is greater than

1:1 and less than 2:1, and in which

Z is halogen, in particular chlorine, and

R₁, R₂, A₁, A₂ and X₁ are as defined under the formulae (1a) and (2a).

The compound of the formula (16) can advantageously be obtained as described above.

The reaction of the compound of the formula (16) with the compound of the formula (17) is carried out, for example, at an elevated temperature, preferably 70° to 100° C., and at an alkaline pH, which is, for example, 9 to 12, depending on the compound of the formula (17) employed. The compounds of the formulae (16) and (17) are employed here in a molar ratio which is greater than 1:1 and less than 2:1. The compounds of the formulae (16) and (17) are preferably employed here in a molar ratio of 9:8 to 15:8, in particular in a molar ratio of 10:8 to 14:8. In contrast to the process for the preparation of the compounds of the formula (1) in which n is the number 0, a pH which is more in the alkaline range furthermore is used in the process for the preparation of the dye mixtures of the compounds of the formulae (1a) and (2a).

The radicals R₁, R₂, R₃, R₄, R₅, R₆, B₁, B₂, A₁, A₂, A₃, A₄, A₅, A₆, Y₁ and Y₂ of compounds employed in the above processes are as defined and preferred above.

The compounds employed in the above processes are known or can be obtained analogously to known compounds.

The compounds of the formulae (19a) to (19f) can be obtained in a known manner by diazotization and coupling of corresponding starting compounds, the diazotization being carded out in a manner known per se, for example with a nitrite, for example with an alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, for example in a hydrochloric acid medium, at temperatures of, for example, -5° to 40° C., and preferably at -5° to 10° C. The coupling is carded out in a manner known per se at acid, neutral to weakly alkaline pH values and at temperatures of, for example, 0° to 30° C.

If the compounds of the formulae (19a) to (19f) are metal complex azo compounds, these can be obtained from the corresponding azo compounds by customary metallization reactions.

The dye mixtures according to the invention of the anionic acid dyes of the formulae (1) and (2) can also be prepared, for example, by mixing the individual dyes. This mixing process is carded out, for example, in suitable mills, for example bead and pinned disc mills, as well as in kneaders or mixers.

The dye mixtures furthermore can be prepared, for example, by spray drying the aqueous dye mixtures.

The dye mixtures preferably comprise 5 to 95% by weight, in particular 10 to 90% by weight, and preferably 20 to 80% by weight, of a dye of the formula (1), based on the total amount of dyes in the mixture.

The anionic acid dyes of the formulae (1) and (2) are present either in the form of their free acid or, preferably, as salts thereof.

Salts are, for example, the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples are the sodium, lithium, potassium or ammonium salts or the salt of mono-, di- or triethanolamine.

The term sulfo generally includes the free acid form (--SO₃ H) as well as the salt form.

The dyes of the formulae (1) and (2) are anionic acid dyes. In these, the number of anionic groups, in particular the number of sulfo groups, is greater than the number of cationic groups. Cationic groups are to be understood as meaning those which carry a cationic charge under the customary dyeing conditions. Examples are aliphatically bonded amino radicals. The nitrogen atoms present in the triazine ring and those bonded to the triazine radical carry no cationic charge.

The invention furthermore relates to the use of the anionic acid dyes of the formulae (1) and (2) and mixtures thereof for dyeing or printing fibre materials containing nitrogen groups and, in particular, fibre materials containing hydroxyl groups.

The anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof are therefore suitable for dyeing and printing nitrogen-containing or, in particular, cellulosic fibre materials, preferably textile fibre materials, of silk, wool or synthetic polyamides, and preferably of cellulosic fibres, such as rayon, cotton or hemp. Paper and leather may also be mentioned.

As regards their dyeing properties, they can be described as directly absorbing or direct dyes (C.I. direct dyes).

Textile fibre materials comprising blends, for example of wool/cotton, polyamide/cotton, polyacrylic/cotton or, in particular, polyester/cotton blends, can likewise be dyed by one-bath dyeing processes and in the presence of dyes for the other respective fibre types.

The textile fibre materials can be in widely varying states of processing, for example as fibres, yarn, woven fabric or knitted fabric.

Level dyeings having good all-round properties, in particular good fastnesses to rubbing, wet processing, wet rubbing, perspiration and light, are obtained. If necessary, the wet fastness properties, in particular the fastness to washing, of the resulting direct dyeings and prints can be further improved substantially by an after-treatment with so-called fixing agents.

The anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof can easily be combined with other dyes, in particular disperse dyes. The anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof have an adequate high temperature stability and can thus be used for dyeing under the dyeing conditions for polyester fibres, i.e. at temperatures in the range from about 100° to 150° C., preferably from 110° to 130° C., from an aqueous liquor and at a pH of 4 to 7.5, preferably 5 to 7.

It is thus possible to employ customary disperse dyes together with the anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof in a one-stage, one-bath process for dyeing polyester/cotton blends (blend fabrics), both types of fibre being dyed in a level and fast manner by the particular dye. If a disperse dye with the same shade as the anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof is used, it is also possible to obtain solid dyeings.

By providing the anionic acid dyes of the formulae (1) and (2) according to the invention and mixtures thereof, dyeing of textile blends (blend fabrics), for example those of polyester fibres and cellulose fibres, can be simplified substantially. The dyeing, which is customary per se, of each type of fibre of a fibre mixture in a separate working operation using different dyeing conditions is therefore no longer necessary.

The following examples serve to illustrate the invention. Parts and percentages relate to the weight, unless stated otherwise. Parts by weight and parts by volume bear the same relationship to one another as the kilogram to the liter. Temperatures are in degrees Celsius.

EXAMPLE 1

a) 20.3 parts of cyanuric chloride, 100 parts of water and 100 parts of ice are ground in a mixer. The suspension thus obtained is diluted with 200 parts of water and initially introduced into the reaction vessel.

A solution of 670 parts of water and 46.4 parts of a compound which, in the form of the free acid, has the formula ##STR33## is then added dropwise at a temperature of 0° to 5° C., in the course of 1.5 hours, to the cyanuric chloride suspension obtained as described above. During this operation, the pH is kept at a value of 2.5 to 3 by addition of a 2 normal aqueous sodium hydroxide solution. The mixture is then allowed to react completely for one hour. The solution thus obtained contains the compound, shown in the form of the free acid, of the formula ##STR34##

The compound of the formula (102) can be isolated by salting out, or advantageously employed directly as a solution for a further condensation reaction.

b) A solution of 570 parts of water and 46.4 pans of the compound of the formula (101) is added to the solution, obtainable as described above under a), of the compound of the formula (102) and the pH is brought to a value of 6.5. The temperature is then increased to 40° to 50° C., the pH being kept at a value of 6.5 by addition of a 2 normal aqueous sodium hydroxide solution. After about 13 hours, the condensation reaction has ended. The solution thus obtained contains the compound shown in the form of the free acid, of the formula ##STR35##

The compound of the formula (103) can be isolated by salting out by means of sodium chloride/potassium chloride, or employed directly as a solution for a further condensation reaction.

c) 200 parts of water are added to 14.71 parts of the compound of the formula (103) with a content of 69.2% which is previously separated off by salting out from the solution obtainable as described above under b), and the mixture is heated to a temperature of 85° C.

A solution of 30 parts of water and 1.53 parts of 1,3-diaminopropane, brought to a pH of 8.5 by addition of 2 normal hydrochloric acid, is then added to the solution, prepared as above under c), of the compound of the formula (103). The mixture is heated at a temperature of 85° C. for 4 hours and the pH is kept at a value of 8.5 by addition of a 2 normal aqueous sodium hydroxide solution. To separate off the product, 25 parts of sodium chloride are sprinkled in and the pH is simultaneously brought stepwise to a value of 7 by addition of acetic acid. The mixture is then allowed to cool to a temperature of 30° C. and the dye which has precipitated out is filtered off with suction. After drying, a dye which, in the form of the free acid, is the compound of formula ##STR36## is obtained. The dye of the formula (104) dyes cotton in red colour shades.

EXAMPLE 2

a) 27.7 parts of cyanuric chloride, 100 parts of water and 100 parts of ice are ground in a mixer. The suspension thus obtained is initially introduced into the reaction vessel.

A solution, brought to a pH of 5, of 3000 parts of water and 91 parts of a compound which, in the form of the free acid, has the formula ##STR37## is then added at a temperature of 0° to 5° C., in the course of one hour, to the cyanuric chloride suspension obtained as described above. During this operation, the pH is kept at a value of 2 by addition of a 2 normal aqueous sodium hydroxide solution. The pH is then brought to a value of 5 and the mixture is allowed to react completely at the pH of 5 and at room temperature for about 4 hours. The solution thus obtained contains the compound, shown in the form of the free acid, of the formula ##STR38##

b) A solution is prepared which contains 2000 parts of water and 91 parts of the compound, shown in the form of the free acid, of the formula ##STR39## and is brought to a pH of 6.

This solution of the compound of the formula (107) is added dropwise at room temperature, in the course of one hour, to the solution, obtainable as described above under a), of the compound of the formula (106), the pH being kept at a value of 5.7 by addition of a 2 normal aqueous sodium carbonate solution. The temperature is then increased to 52° to 55° C. and the pH is further kept at a value of 5.7. The mixture is allowed to react completely for 20 hours. It is then cooled to a temperature of 50° C. and the product is salted out with 500 pans of sodium chloride, and 1200 parts of ethanol are added dropwise to bring the separation to completion. The mixture is stirred thoroughly for a further 2 hours and the product which has precipitated out is filtered off with suction. After drying, a compound which, in the form of the free acid, has the formula ##STR40## is obtained.

c) 180 parts of water are added to 13.13 parts of the compound of the formula (108) obtainable as described under b), with a content of 75.7 %. This solution is brought to a pH of 6 and heated to a temperature of 85° C.

A solution of 20 parts of water and 1.46 parts of 1-(2-aminoethyl)-piperazine, which is brought to a pH of 6.5 by addition of concentrated hydrochloric acid, is then added to the solution, prepared as above under c), of the compound of the formula (108). The mixture is heated at a temperature of 85° C. for 15 hours and the pH is kept at a value of 6.5 by addition of a 1 normal aqueous sodium hydroxide solution. The reaction solution thus obtained contains the compound, shown in the form of the free acid, of the formula ##STR41##

d) To split off the sulfonic acid ester of the compound of the formula (109), 11 parts of an aqueous sodium hydroxide solution (30% strength) are added at a temperature of 85° C. to the solution, obtainable as described above under c), of the compound of the formula (109) and the mixture is allowed to react for about 2 to 3 hours. It is then brought to a pH of 9 with a 2 normal aqueous hydrochloric acid solution and the product which has precipitated out is filtered off and dried. A dye which, in the form of the free acid, is the compound of the formula ##STR42## is obtained. The dye of the formula (110) dyes cotton in red shades.

Radicals A₁ and A₂ listed in the following tables are identified by the symbols A to Z6 and have the following meanings there: ##STR43##

Bridge members B₁ listed in the following tables are identified by the symbols a to 1 and have the following meanings there: ##STR44##

EXAMPLES 3 to 104: Dyes of the general formula ##STR45## in which A₁, A₂ and Y₁ are as defined in the following Table 1, can be obtained in an analogous manner to Examples 1 and 2. The dyes shown in the form of the free acid in Table 1 dye cotton in the colour shades stated in column 5 of the table.

The symbols A to Z6 for the radicals A1 and A₂ are as defined above.

                                      TABLE 1                                      __________________________________________________________________________     Example                                                                             A.sub.1                                                                           A.sub.2                                                                           Y.sub.1            Shade on cotton                                  __________________________________________________________________________     3    A  A  NHCH.sub.2 CH.sub.2NH.sub.2                                                                       scarlet                                          4    A  A                                                                                  ##STR46##         scarlet                                          5    A  A                                                                                  ##STR47##         scarlet                                          6    A  A                                                                                  ##STR48##         scarlet                                          7    A  A                                                                                  ##STR49##         scarlet                                          8    A  A                                                                                  ##STR50##         scarlet                                          9    A  A                                                                                  ##STR51##         scarlet                                          10   A  A                                                                                  ##STR52##         scarlet                                          11   A  A                                                                                  ##STR53##         scarlet                                          12   A  F  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              red                                              13   A  F                                                                                  ##STR54##         red                                              14   A  F                                                                                  ##STR55##         red                                              15   A  F                                                                                  ##STR56##         red                                              16   F  F  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                17   F  F                                                                                  ##STR57##         bluish-tinged red                                18   F  I                                                                                  ##STR58##         bluish-tinged red                                19   F  I                                                                                  ##STR59##         bluish-tinged red                                20   F  I  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                21   F  I                                                                                  ##STR60##         bluish-tinged red                                22   F  I                                                                                  ##STR61##         bluish-tinged red                                23   F  I                                                                                  ##STR62##         bluish-tinged red                                24   F  I                                                                                  ##STR63##         bluish-tinged red                                25   F  I  NH(CH.sub.2).sub.5NH.sub.2                                                                        bluish-tinged red                                26   F  I                                                                                  ##STR64##         bluish-tinged red                                27   F  I                                                                                  ##STR65##         bluish-tinged red                                28   I  I  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           29   I  I                                                                                  ##STR66##         orange                                           30   I  A  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              scarlet                                          31   I  A                                                                                  ##STR67##         scarlet                                          32   I  A                                                                                  ##STR68##         scarlet                                          33   B  A                                                                                  ##STR69##         red                                              34   B  A                                                                                  ##STR70##         red                                              35   M  M  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              pink                                             36   M  M                                                                                  ##STR71##         pink                                             37   M  G  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              pink                                             38   M  G                                                                                  ##STR72##         pink                                             39   M  F  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                40   M  F                                                                                  ##STR73##         bluish-tinged red                                41   M  H  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                42   Q  H  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              claret-brown                                     43   Q  H                                                                                  ##STR74##         claret-brown                                     44   Q  G  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              claret                                           45   Q  G                                                                                  ##STR75##         claret                                           46   Q  F                                                                                  ##STR76##         claret                                           47   Q  F  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              claret                                           48   Q  N  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              claret                                           49   N  N                                                                                  ##STR77##         bluish-tinged red                                50   Q  V                                                                                  ##STR78##         claret                                           51   Q  V  NH(CH.sub.2).sub.4NH.sub.2                                                                        claret                                           52   Q  V                                                                                  ##STR79##         claret                                           53   Q  Q  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              claret                                           54   Q  Q                                                                                  ##STR80##         claret                                           55   Q  Q                                                                                  ##STR81##         claret                                           56   I  Q                                                                                  ##STR82##         brown-claret                                     57   C  Q  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              scarlet-orange                                   58   R  Q                                                                                  ##STR83##         brown                                            59   D  V  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              pink                                             60   D  V                                                                                  ##STR84##         pink                                             61   D  P                                                                                  ##STR85##         red-violet                                       62   D  P  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              red-violet                                       63   D  S                                                                                  ##STR86##         brown-orange                                     64   X  E                                                                                  ##STR87##         brown-red                                        65   X  X  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              brown-red                                        66   X  Q  NH(CH.sub.2).sub.6NH.sub.2                                                                        brown-claret                                     67   X  F  NH(CH.sub.2).sub.4NH.sub.2                                                                        brown                                            68   X  K  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              brown                                            69   X  M                                                                                  ##STR88##         brown                                            70   X  T  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              brown-orange                                     71   O  T  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           72   W  T  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           73   J  T  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           74   F  T  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           75   I  Y  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange                                           76   L  P                                                                                  ##STR89##         red                                              77   L  P                                                                                  ##STR90##         red                                              78   L  P                                                                                  ##STR91##         red                                              79   L  O  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              red                                              80   L  O                                                                                  ##STR92##         red                                              81   V  M  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              pink                                             82   V  V  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              red                                              83   V  V                                                                                  ##STR93##         red                                              84   V  V                                                                                  ##STR94##         red                                              85   V  I  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                86   V  Z  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              orange-red                                       87   V  F  NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                88   V  F                                                                                  ##STR95##         bluish-tinged red                                89   V  F                                                                                  ##STR96##         bluish-tinged red                                90   Z2 Z2 NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              scarlet                                          91   Z2 Z2                                                                                 ##STR97##         scarlet                                          92   Z2 Z2                                                                                 ##STR98##         scarlet                                          93   Z2 Z2                                                                                 ##STR99##         scarlet                                          94   Z2 Z2                                                                                 ##STR100##        scarlet                                          95   Z2 Z2                                                                                 ##STR101##        scarlet                                          96   Z2 Z2                                                                                 ##STR102##        scarlet                                          97   Z2 Z2                                                                                 ##STR103##        scarlet                                          98   Z2 Z2                                                                                 ##STR104##        scarlet                                          99   Z5 Z5 NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              bluish-tinged red                                100  Z5 Z5                                                                                 ##STR105##        bluish-tinged red                                101  Z5 Z5                                                                                 ##STR106##        bluish-tinged red                                102  Z4 Z4 NHCH.sub.2 CH.sub.2 CH.sub.2NH.sub.2                                                              brown                                            103  Z4 Z4                                                                                 ##STR107##        brown                                            104  Z4 Z4                                                                                 ##STR108##        brown                                            __________________________________________________________________________

EXAMPLE 105:

a) 20.3 parts of cyanuric chloride, 100 parts of water and 100 parts of ice are ground in a mixer. The suspension thus obtained is diluted with 200 parts of water and initially introduced into the reaction vessel.

A solution of 670 parts of water and 46.4 parts of a compound which, in the form of the free acid, has the formula ##STR109## is then added dropwise at a temperature of 0° to 5° C., in the course of 1.5 hours, to the cyanuric chloride suspension obtained as described above. During this operation, the pH is kept at a value of 2.5 to 3 by addition of a 2 normal aqueous sodium hydroxide solution. The mixture is then allowed to react completely for one hour. The solution thus obtained contains the compound, shown in the form of the free acid, of the formula ##STR110##

The compound of the formula (102) can be isolated by salting out, or advantageously employed directly as a solution for a further condensation reaction.

b) 5.4 parts of 1,4-diaminobenzene are added to the solution, obtainable as described above under a), of the compound of the formula (102) and the mixture is heated to a temperature of 40° C. The pH is kept at a value of 6.5 by addition of a 2 normal aqueous potassium bicarbonate solution and the mixture is allowed to react completely for about 18 to 20 hours. The solution thus obtained contains the compound, shown in the form of the free acid, of the formula ##STR111## in which

A₁ is a radical of the formula ##STR112##

The compound of the formula (111) can be separated off by means of sodium chloride and by addition of ethanol, or advantageously employed directly as a solution for a further condensation reaction.

c) A solution of 150 parts of water and 22.2 parts of 1,3-diaminopropane, which has first been brought to a pH of 8.5 by addition of a 2 normal hydrochloric acid solution, is added to the solution, obtainable as described above under b), of the compound of the formula (111) and the mixture is then heated to a temperature of 80° C. During this operation, the pH is kept constant at a value of 8.5. The mixture is allowed to react completely for 20 hours, the pH is brought to a value of 7 and the product is salted out with an aqueous sodium chloride solution (10% strength). The resulting product is filtered off with suction and dried. A dye which, in the form of the free acid, has the formula ##STR113## in which

A₁ is the radical of the formula (112) defined above, is obtained. The dye of the formula (113) dyes cotton in red shades.

EXAMPLES 106 to 164: Dyes of the general formula ##STR114## in which

A₁, A₂, B₁ and Y₁ are as defined in the following Table 2, can be obtained in an analogous manner to Example 105. The dyes shown in the form of the free acid in Table 2 dye cotton in the shades stated in column 6 of Table 2.

The symbols A to Z6 for the radicals A₁ and A₂ and the symbols a to h for bridge member B₁ are as defined above.

                  TABLE 2                                                          ______________________________________                                         Ex-                                      Shade                                 am-                                      on                                    ple  A.sub.1                                                                              A.sub.2                                                                              B.sub.1                                                                            Y.sub.1             cotton                                ______________________________________                                         106  A     A     b                                                                                   ##STR115##         scarlet                               107  A     A     c                                                                                   ##STR116##         scarlet                               108  F     F     a                                                                                   ##STR117##         bluish- tinged red                    109  F     F     d                                                                                   ##STR118##         bluish- tinged red                    110  I     I     e   NHCH.sub.2 CH.sub.2 NH.sub.2                                                                       orange                                111  B     B     a                                                                                   ##STR119##         pink                                  112  B     B     b                                                                                   ##STR120##         pink                                  113  M     M     c                                                                                   ##STR121##         pink                                  114  M     M     c   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              pink                                  115  M     M     c                                                                                   ##STR122##         pink                                  116  Q     Q     c   NH(CH.sub.2).sub.4 NH.sub.2                                                                        claret                                117  N     N     f                                                                                   ##STR123##         pink                                  118  Q     Q     g   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              claret                                119  N     N     g                                                                                   ##STR124##         pink                                  120  Q     Q     h                                                                                   ##STR125##         claret                                121  R     R     c                                                                                   ##STR126##         lemon yellow                          122  E     E     c   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              pink                                  123  E     E     c                                                                                   ##STR127##         pink                                  124  E     E     c                                                                                   ##STR128##         pink                                  125  E     E     c                                                                                   ##STR129##         pink                                  126  X     X     a   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              brown                                 127  X     X     b                                                                                   ##STR130##         brown                                 128  X     X     c                                                                                   ##STR131##         brown                                 129  V     V     c                                                                                   ##STR132##         red                                   130  V     V     c   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              red                                   131  V     V     c                                                                                   ##STR133##         red                                   132  V     V     a                                                                                   ##STR134##         red                                   133  V     V     b                                                                                   ##STR135##         red                                   134  V     V     b   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              red                                   135  Z2    Z2    a   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              orange                                136  F     F     b   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              red                                   137  I     F     b                                                                                   ##STR136##         red                                   138  Z5    Z5    a                                                                                   ##STR137##         bluish- tinged red                    139  Z1    Z5    a                                                                                   ##STR138##         bluish- tinged red                    140  Z5    Z5    a   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   141  Z5    Z5    a                                                                                   ##STR139##         bluish- tinged red                    142  Z5    Z5    b   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   143  Z5    Z5    b                                                                                   ##STR140##         bluish- tinged red                    144  Z5    Z5    b   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   145  Z5    Z5    b                                                                                   ##STR141##         bluish- tinged red                    146  Z5    Z5    g                                                                                   ##STR142##         bluish- tinged red                    147  Z5    Z5    g   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   148  Z5    Z5    g                                                                                   ##STR143##         bluish- tinged red                    149  Z5    Z5    g                                                                                   ##STR144##         bluish- tinged red                    150  Z6    Z6    a   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   151  Z6    Z6    b                                                                                   ##STR145##         bluish- tinged red                    152  Z6    Z6    g                                                                                   ##STR146##         bluish- tinged red                    153  Z6    Z6    g   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              bluish-                                                                        tinged                                                                         red                                   154  X     X     a                                                                                   ##STR147##         brown                                 155  X     X     b                                                                                   ##STR148##         brown                                 156  X     X     g   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              brown                                 157  X     X     g                                                                                   ##STR149##         brown                                 158  Z4    Z4    a                                                                                   ##STR150##         brown                                 159  Z4    Z4    b                                                                                   ##STR151##         brown                                 160  Z4    Z4    c   NHCH.sub.2 CH.sub.2 NH.sub.2                                                                       brown                                 161  Z4    Z4    c                                                                                   ##STR152##         brown                                 162  Z4    Z4    c                                                                                   ##STR153##         brown                                 163  Z4    Z4    g                                                                                   ##STR154##         brown                                 164  Z4    Z4    g   NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                              brown                                 ______________________________________                                    

EXAMPLE 165

The procedure is as described in Steps a) and b) of Example 1 and the compound of the formula (103) is then salted out.

500 parts of water are added to 14.71 parts of the compound of the formula (103) thus obtainable, which has a content of 69.2%, and the mixture is initially introduced into the reaction vessel. 0.38 part of 1,3-diaminopropane is then added and the reaction solution is left at a temperature of 85° C. for about 20 hours, the pH being kept constant at a value of about 8.3 to 8.4 by addition of a 2 normal aqueous sodium hydroxide solution. The resulting product is separated out by addition of 50 parts of sodium chloride, filtered off and dried. A dye which, in the form of the free acid, has the formula ##STR155## in which

A₁ is a radical of the formula ##STR156## is obtained. The dye of the formula (114) dyes cotton in red shades.

EXAMPLE 116

The procedure is as described in steps a) and b) of Example 1, and 5.4 parts of 1,4-diaminobenzene are added to the resulting solution of the compound of the formula (103). The reaction solution is then left at a temperature of 80° C. for about 20 hours, the pH being kept constant at a value of about 6 to 7 by addition of a 2 normal aqueous sodium hydroxide solution. For separation, the product is salted out by addition of potassium chloride. The resulting product is then filtered off with suction and dried. A dye which, in the form of the free acid, has the formula ##STR157## in which

A₁ is a radical of the formula ##STR158## is obtained. The dye of the formula (115) dyes cotton in red shades.

EXAMPLES 167 to 180

Dyes of the general formula ##STR159## in which

A₁, A₂ and B₁ are as defined in the following Table 3, can be obtained in an analogous manner to Example 165 or 166. The dyes shown in the form of the free acid in Table 3 dye cotton in the shades stated in column 5 of Table 3.

The symbols A to Z6 for the radicals A₁ and A₂ and the symbols a to 1 for the bridge members B₁ are as defined above.

                  TABLE 3                                                          ______________________________________                                         Ex-                                                                            ample     A.sub.1 A.sub.2 B.sub.1                                                                              Shade on cotton                                ______________________________________                                         167       A       A       b     scarlet                                        168       A       A       i     scarlet                                        169       A       A       j     scarlet                                        170       A       A       h     scarlet                                        171       A       A       k     scarlet                                        172       A       F       i     red                                            173       I       F       i     bluish-tinged red                              174       I       F       l     bluish-tinged red                              175       I       F       a     bluish-tinged red                              176       M       F       i     bluish-tinged red                              177       M       M       i     bluish-tinged red                              178       Q       F       l     claret                                         179       X       T       i     brown-orange                                   180       Z1      Z1      l     golden yellow                                  ______________________________________                                    

EXAMPLE 181: The procedure is as described in steps a) and b) of Example 1 and the compound of the formula (103) is salted out.

150 parts of water are added to 14.71 parts of the compound of the formula (103) thus obtainable, which has a content of 69.2%, and the mixture is heated to a temperature of 85° C.

1.33 parts of 1,3-diaminopropane are then added, the pH rising to a value of about 10.5. The reaction solution is then heated at a temperature of 83° to 85° C. for about 18 hours. The pH is subsequently brought slowly to a value of 4.5 by means of acetic acid and the product which has precipitated out is filtered off with suction at a temperature of 60° C. and then dried. A dye mixture which comprises dyes, shown in the form of the free acids, of the formulae ##STR160## in a ratio of about 3:1, in which

A₁ is a radical of the formula ##STR161## is obtained. The mixture of the dyes of the formulae (116) and (114) dyes cotton in red shades.

EXAMPLES 182 to 205: Dye mixtures which comprise a dye of the general formula ##STR162## together with a dye of the general formula ##STR163## in which

A₁, B₁ and Y₁ are as defined in the following Table 4, can be obtained in an analogous manner to Example 181. The dye mixtures shown in the form of the free acid in Table 4 dye cotton in the shades stated in column 5 of Table 4.

The symbols A to Z6 for the radicals A₁ are as defined above.

                                      TABLE 4                                      __________________________________________________________________________     Example                                                                             A.sub.1                                                                          B.sub.1          Y.sub.1         Shade on cotton                        __________________________________________________________________________     182  A                                                                                 ##STR164##                                                                                      ##STR165##     scarlet                                183  A                                                                                 ##STR166##                                                                                      ##STR167##     scarlet                                184  A                                                                                 ##STR168##                                                                                      ##STR169##     scarlet                                185  A NHCH.sub.2 CH.sub.2 NH                                                                          NHCH.sub.2 CH.sub.2 NH.sub.2                                                                   scarlet                                186  F NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          bluish-tinged red                      187  F                                                                                 ##STR170##                                                                                      ##STR171##     bluish-tinged red                      188  F                                                                                 ##STR172##                                                                                      ##STR173##     bluish-tinged red                      189  I NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          orange                                 190  B NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          pink                                   191  B                                                                                 ##STR174##                                                                                      ##STR175##     pink                                   192  M NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          pink                                   193  M                                                                                 ##STR176##                                                                                      ##STR177##     pink                                   194  Q NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          claret                                 195  Q                                                                                 ##STR178##                                                                                      ##STR179##     claret                                 196  R NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          lemon yellow                           197  E NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          pink                                   198  X NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          brown                                  199  X                                                                                 ##STR180##                                                                                      ##STR181##     brown                                  200  Y NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          orange                                 201  Y                                                                                 ##STR182##                                                                                      ##STR183##     orange                                 202  U NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          lemon yellow                           203  U                                                                                 ##STR184##                                                                                      ##STR185##     lemon yellow                           204  Z1                                                                               NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                                 NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2                                                          golden yellow                          205  Z1                                                                               NHCH.sub.2 CH.sub.2 NH                                                                          NHCH.sub.2 CH.sub.2 NH.sub.2                                                                   golden yellow                          __________________________________________________________________________

EXAMPLES 206 to 226: In each case 100 parts of the dye mixtures shown in the following Table 5, which dye cotton in the shades shown in the last column of Table 5, are prepared by mixing in a mixer.

                                      TABLE 5                                      __________________________________________________________________________                                  Shade                                             Example                                                                             Dye mixture             on cotton                                         __________________________________________________________________________     206  Mixture of                                                                     75 parts of the dye according to Example 1 and                                                         scarlet                                                25 parts of the dye according to Example 168                              207  Mixture of                                                                     50 parts of the dye according to Example 1 and                                                         scarlet                                                50 parts of the dye according to Example 168                              208  Mixture of                                                                     60 parts of the dye according to Example 1 and                                                         scarlet                                                40 parts of the dye according to Example 169                              209  Mixture of                                                                     85 parts of the dye according to Example 1 and                                                         scarlet                                                15 parts of the dye according to Example 169                              210  Mixture of                                                                     70 parts of the dye according to Example 1 and                                                         scarlet                                                30 parts of the dye according to Example 170                              211  Mixture of                                                                     50 parts of the dye according to Example 1 and                                                         scarlet                                                50 parts of the dye according to Example 170                              212  Mixture of                                                                     25 parts of the dye according to Example 12 and                                                        red                                                    75 parts of the dye according to Example 172                              213  Mixture of                                                                     15 parts of the dye according to Example 70 and                                                        red                                                    85 parts of the dye according to Example 179                              214  Mixture of                                                                     95 parts of the dye according to Example 39 and                                                        bluish-tinged red                                      5 parts of the dye according to Example 176                               215  Mixture of                                                                     5 parts of the dye according to Example 47 and                                                         bluish-tinged red                                      95 parts of the dye according to Example 178                              216  Mixture of                                                                     30 parts of the dye according to Example 20 and                                                        bluish-tinged red                                      70 parts of the dye according to Example 173                              217  Mixture of                                                                     90 parts of the dye according to Example 18 and                                                        bluish-tinged red                                      10 parts of the dye according to Example 174                              218  Mixture of                                                                     10 parts of the dye according to Example 35 and                                                        bluish-tinged red                                      90 parts of the dye according to Example 177                              219  Mixture of                                                                     70 parts of the dye according to Example 18 and                                                        bluish-tinged red                                      30 parts of the dye according to Example 174                              220  Mixture of                                                                     55 parts of the dye according to Example 114 and                                                       pink                                                   45 parts of the dye according to Example 177                              221  Mixture of                                                                     50 parts of the dye according to Example 39 and                                                        bluish-tinged red                                      50 parts of the dye according to Example 176                              222  Mixture of                                                                     80 parts of the dye according to Example 114 and                                                       pink                                                   20 parts of the dye according to Example 177                              223  Mixture of                                                                     60 parts of the dye according to Example 47 and                                                        claret                                                 40 parts of the dye according to Example 184                              224  Mixture of                                                                     50 parts of the dye according to Example 20 and                                                        bluish-tinged red                                      50 parts of the dye according to Example 173                              225  Mixture of                                                                     40 parts of the dye according to Example 12 and                                                        red                                                    60 parts of the dye according to Example 172                              226  Mixture of                                                                     50 parts of the dye according to Example 70 and                                                        brown-orange                                           50 parts of the dye according to Example 179                              __________________________________________________________________________

Dyeing instructions 1

10 parts of cotton fabric (bleached and mercerized) are introduced at about 30° C. into a dyebath which comprises 200 parts of water and 0.35 part of the dye of Example 1. The liquor is heated to 95° C. in the course of 30 minutes and left at this temperature for 15 minutes. 4 parts of sodium sulfate are then added and dyeing is continued at 95° C. for a further 45 minutes. Thereafter, the dyebath is cooled to 80° C. in the course of 15 minutes and left at this temperature for a further 15 minutes. The dyeing is then rinsed thoroughly with cold water and dried.

Dyeing instructions 2

10 parts of a fibre mixture of polyester and cotton are introduced at about 50° C. into a dyebath which comprises 200 parts of water, a dye mixture comprising 0.2 part of C.I. Direct Red 60 and 0.2 part of the dye mixture according to Example 181, 0.4 part of ammonium sulfate and 0.2 part of an anionic dispersant (for example formaldehyde condensation product of naphthalenesulfonic acid). The dyebath is brought to a pH of 5.5 with formic acid, 1 part of sodium sulfate is added and the bath is then heated to about 130° C. in the course of 45 minutes. Dyeing is continued at 130° C. for 45 minutes and the dyebath is then cooled to about 80° C. in the course of 30 minutes and left at this temperature for a further 45 minutes. The dyeing is then rinsed thoroughly with cold water and dried.

Dyeing instructions 3

The procedure is as described in dyeing instructions 1 or 2, but after the dyeing operation has ended, the dyeing, which has been rinsed cold, is introduced into a fresh bath, heated at about 30° C., which comprises 200 parts of water and 0.2-0.6 part of a cationic after-treatment agent (amine-formaldehyde dicyandiamide condensation product or formulation based on dicyandiamide and diethylenetriamine). The dyeing is after-treated at 30° C. for 30 minutes and then dried without a further rinsing process; a dyeing having improved wet fastness properties is obtained.

Dyeing instructions 4

The procedure is as described in dyeing instructions 1 or 2, but after the dyeing operation has ended, the dyeing, which has been rinsed cold, is introduced into a fresh bath, heated at about 25° C., which comprises 200 parts of water, 1 part of sodium sulfate and 0.6 part of a fibre-reactive cationic after-treatment agent based on N-methyldialkylamine and epichlorohydrin. The temperature is increased to 40° C. in the course of 15 minutes, 0.8 part of 30% sodium hydroxide solution is added and the dyeing is treated at 40° C. for a further 45 minutes. The dyeing is then rinsed hot and dried; it has improved wet fastness properties. 

What is claimed is:
 1. An anionic acid dye of the formula ##STR186## in which R₁ and R₂ independently of one another are hydrogen or C₁ -C₄ alkyl,B₁ is an aliphatic or aromatic bridge member, A₁ and A₂ independently of one another are the radical of a monoazo- or disazo dye or the radical of a metal complex azo dye, n is the number 0 or 1 and Y₁ and Y₂ independently of one another are a radical of the formula ##STR187## in which R₇, R₈ and R₈ ' independently of one another are hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted by hydroxyl, C₁ -C₄ alkoxy, halogen, amino or sulfato, and E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl, C₁ -C₄ alkoxy, halogen, amino or sulfato and is uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene, each of which is unsubstituted or substituted in the alkylene radical by hydroxyl or C₁ -C₄ alkoxy and in the cycloalkyl ring by C₁ -C₄ alkyl, and in which dye of formula (1) the number of sulfo groups is greater than the number of cationic groups and basic groups.
 2. An anionic acid dye according to claim 1, in which R₁ and R₂ are hydrogen.
 3. An anionic acid dye according to claim 1, in which B₁ is a bridge member of the formula ##STR188## in which R₉, R₁₀ and R₁₁ independently of one another are hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy,R₁₂ and R₁₂ ' independently of one another are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen, suffo or carboxyl and E₂ and E₃ independently of one another are C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene which are unsubstituted or substituted by C₁ -C₄ alkyl in the cycloalkyl ting.
 4. An anionic acid dye according to claim 1, in whichn is the number
 0. 5. An anionic acid dye according to claim 1, in which R₇, R₈ and R₈ ' independently of one another are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and uninterrupted or interrupted by one or more groups -O-, or C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-C₁ -C₈ alkylene or C₁ -C₈ alkylene-C₅ -C₇ cycloalkylene which are unsubstituted or substituted by C₁ -C₄ alkyl in the cycloalkyl ring.
 6. An anionic acid dye according to claim 1, in which A₁ and A₂ independently of one another are a radical of the formula ##STR189## in which R₁₃, R₁₄, R₁₅ and R₁₆ independently of one another are hydrogen, sulfo, carboxyl, carbamoyl, halogen, cyano or ureido, C₁ -C₄ alkyl or C₁ -C₄ alkoxy which are unsubstituted or substituted by hydroxyl, or C₂ -C₄ alkanoylamino which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy in the alkyl part; ##STR190## in which R₁₇, R₁₈ and R₁₉ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR191## in which R₂₀, R₂₁, R₂₂, R₂₃ and R₂₄ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR192## in which R₂₅ and R₂₆ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR193## in which R₂₇ is hydrogen, C₂ -C₆ alkanoyl which is unsubstituted or substituted by hydroxyl orC₁ -C₄ alkoxy, or phenyl or benzoyl which are unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, sulfo, carboxyl, halogen, cyano or ureido in the phenyl ring, and R₂₈ and R₂₉ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR194## in which R₃₀ and R₃₁ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR195## in which R₃₂ and R₃₃ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; ##STR196## in which R₃₄, R₃₅, R₃₆ and R₃₇ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆ ; or ##STR197## in which R₃₈, R₃₉, R₄₀, R₄₁, R₄₂ and R₄₃ have the definitions assigned above to R₁₃, R₁₄, R₁₅ and R₁₆.
 7. An anionic acid dye according to claim 6, in which A₁ and A₂ independently of one another are a radical of the formula (6), (7), (8), (9), (10), (11), (12) or (14).
 8. An anionic acid dye according to claim 6, in whichn is the number 0, R₇, R₈ and R₈ ' are hydrogen or C₁ -C₄ alkyl which is unsubstituted or substituted by hydroxyl or C₄ -C₄ alkoxy,E₁ is C₂ -C₈ alkylene which is unsubstituted or substituted by hydroxyl or C₁ -C₄ alkoxy and A₁ and A₂ independently of one another are a radical of the formula (6), (7), (8), (9), (10), (11), (12) or (14), and A₁ and A₂ have identical meanings. 